Optical brighteners

ABSTRACT

The invention relates to novel bis(triazinylamino)stilbenes which are suitable as UV absorbers and fluorescent whiteners for textile materials and also bring about an increase in the treated textile material.

The present invention relates to novel stilbene derivatives, to aprocess for the preparation of such compounds and to their use in theoptical brightening of textile fibres and paper.

Sulfonic acid derivatives of bis(triazinylamino)stilbenes are among themost commonly used optical brighteners for paper and textiles.

Cationic bis(triazinylamino)stilbenes are frequently used in liquiddetergents on account of their compatibility with cationic ingredients.The known cationic stilbene derivatives can be used only to a limitedextent, however, in the field of textiles on account of their lowsubstantivity for cellulose.

It has now been found that certain amphoteric or cationicbis(triazinylamino)stilbenes exhibit a high brightener action both inpaper manufacture and in textile finishing and when used in detergents.The novel compounds exhibit strong absorption in both the UV-A and theUV-B range and have a high degree of substantivity for cellulose.

The present invention relates to compounds of formula (1), (2) or (3)

wherein

M is hydrogen, an alkali metal ion or an ammonium ion,

A₁ is —OR₁, —NHR₁, N-morpholinyl or 1-piperidyl,

A₂ is —OR₂, —NHR₂, N-morpholinyl or 1-piperidyl,

E₁, E₂, E₃ and E₄ are each independently of the others —O—, —NH— or—NR₉—, wherein R₉ together with R₄, R₆, R₂ or R₁₂ forms an ethyleneradical,

R₁ to R₆, R₁₁ and R₁₂ are each independently of the others hydrogen,alkyl, alkoxy, aryl, aralkyl, alkoxyalkyl, hydroxyalkyl, aminoalkyl or agroup of the formula —(C_(n)H_(2n)Y)_(m)—R₇, wherein Y is —O—, —NH—,—NR₈—, —CONH— or —CONR₈—, R₇ is hydrogen, alkyl or aryl and R₈ is alkylor aryl, n is a number from 2 to 6 and m is a number from 1 to 10, orpairs of two radicals R₁ and R₂, R₃ and R₄, R₅ and R₆ or R₁₁ and R₁₂together form a bivalent radical of the formula —CH₂CH₂OCH₂CH₂— or, whenE₁, E₂, E₃ or E₄ is —NR₉—,

R₄, R₆, R₂ or R₁₂ together with R₉ forms an ethylene radical,

R₁₀, R₁₃, R₁₄ and R₁₅ are each independently of the others alkyl,alkenyl, aryl or aralkyl,

X₁ and X₂ are each independently of the other 1,2-cyclohexanediyl, agroup of the formula —(C_(n)H_(2n))_(m)— or a group of the formula—(C_(n)H_(2n)Y)_(m)—, wherein Y is —O—, —NH—, —NR₈—, —CONH— or —CONR₈—and R₈ is alkyl or aryl, n is a number from 2 to 6 and m is a numberfrom 1 to 10, Y₁ and Y₂ are each independently of the other1,2-cyclohexanediyl, a group of the formula —(C_(n)H_(2n))_(m)— or agroup of the formula —(C_(n)H_(2n)Y)_(m)—, wherein Y is —O—, —NH—,—NR₈—, —CONH— or —CONR₈— and R₈ is alkyl or aryl, n is a number from 2to 6 and m is a number from 1 to 10 and A⁻ is a singly charged anion orthe two A⁻ form a doubly charged anion,

R₁₆, R₁₇, R₁₈ and R₁₉ are each independently of the others hydrogen,2-hydroxyethyl, 2-aminoethyl or 3-aminopropyl,

R₂₀, R₂₁, R₂₂ and R₂₃ are each independently of the others alkyl, and

A₃ and A₄ are 2-hydroxyethylamino, 3-dimethylaminopropylamino or3-diethylaminopropylamino.

The amphoteric compounds of formulae (2) and (3) can be in the form ofinternal or external salts. For example, when M in formula (3) ishydrogen, the compound of formula (3) can be in the form of a mixture ofthe neutral compound and the zwitterion in equilibrium:

M in formula (2) and formula (3) can also be an alkali metal cation,such as Na⁺ or K⁺, or an unsubstituted or substituted ammonium ion, suchas NH₄ ⁺ or N(CH₃)₄ ⁺.

When any radicals in formula (1), (2) or (3) are alkyl, such radicalsare preferably straight-chain or branched C₁–C₁₂alkyl groups. Examplesthereof are methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl,sec-butyl, tert-butyl, amyl, tert-amyl (1,1-dimethylpropyl),1,1,3,3-tetra-methylbutyl, hexyl, 2-methylpentyl, neopentyl,cyclopentyl, cyclohexyl and their respective isomers.

Alkoxy groups are preferably C₁–C₆alkoxy groups, for example methoxy,ethoxy, n-propoxy, isopropoxy, n-butoxy or tert-butoxy.

Aryl radicals in formula (1) or (2) are preferably unsubstituted oralkyl-substituted C₆–C₂₄aryl, for example phenyl, tolyl, mesityl andisityl.

Suitable aralkyl groups preferably contain 6–12 carbon atoms. Examplesthereof are benzyl and 2-phenylethyl.

Suitable alkoxyalkyl groups are, for example, 2-methoxyethyl,2-ethoxyethyl, 3-methoxy-propyl and 3-ethoxypropyl.

Examples of hydroxyalkyl are 2-hydroxyethyl, 3-hydroxypropyl,2-hydroxypropyl, 4-hydroxy-butyl, 3-hydroxybutyl and 2-hydroxybutyl.

Examples of aminoalkyl are 2-aminoethyl, 3-aminopropyl, 2-aminopropyl,4-aminobutyl, 3-aminobutyl and 2-aminobutyl.

Alkenyl groups as radicals R₁₀, R₁₃, R₁₄ or R₁₅ preferably contain 3–6carbon atoms, for example allyl, buten-2-yl and penten-2-yl.

A⁻ in formula (1) is a colourless anion of an inorganic or organic acid.Examples of such anions are halide, such as chloride, bromide or iodide,sulfate, methyl sulfate, tetrafluoroborate, aminosulfonate, perchlorate,carbonate, hydrogen carbonate, benzenesulfonate, naphthalenesulfonate,4-chlorobenzenesulfonate, oxalate, maleate, acetate, propionate,lactate, succinate, chloroacetate, tartrate, methanesulfonate andbenzoate.

Preferred anions are hydrogen sulfate, sulfate, lactate, acetate andespecially chloride and methyl sulfate.

In a preferred embodiment of the invention, the compounds of formulae(2) and (3) are symmetrical; that is to say preference is given tocompounds of formula (2) wherein the substituents A₁ and A₂, E₁ and E₂,X₁ and X₂, R₁₆ and R₁₈ and also R₁₇ and R₁₉ are in each case identical;and compounds of formula (3) wherein the substituents A₃ and A₄, E₁ andE₂, R₂₀ and R₂₂ and also R₂₁ and R₂₃ are in each case identical.

Also preferred are compounds of formula (1) wherein the substituents E₁and E₂, E₃ and E₄, X₁ and X₂, Y₁ and Y₂, R₃ and R₅, R₄ and R₆, R₁₄ andR₁₅, R₁ and R₁₁, R₂ and R₁₂ and also R₁₀ and R₁₃ are in each caseidentical.

In formulae (1) and (2), X₁ and X₂ are preferably ethylene ortrimethylene.

In formula (3), R₂₀, R₂₁, R₂₂ and R₂₃ are preferably methyl or ethyl.

Also preferred are compounds of formula (2) or (3) wherein A₁, A₂, A₃and A₄ are amino, methylamino, 2-hydroxyethylamino,3-dimethylaminopropylamino or ethoxy.

Preference is also given to compounds of formula (1) wherein R₁ to R₆and R₁₀ to R₁₅ are methyl.

The compounds of formulae (1), (2) and (3) according to the inventioncan be synthesised by known methods, starting from cyanuric chloride and4,4′-diaminostilbene-2,2′-disulfonic acid.

The compounds of formula (2) can be prepared, for example, by reactingcyanuric chloride with, in any order,4,4′-diaminostilbene-2,2′-disulfonic acid and compounds of formulae

wherein A₁, A₂, X₁, X₂, E₁, E₂, R₁₆, R₁₇, R₁₈ and R₁₉ are as definedabove.

The compounds of formula (1) can be synthesised analogously, for exampleby reacting cyanuric chloride first with4,4′-diaminostilbene-2,2′-disulfonic acid and a compound of formula

wherein R₂₄ is alkyl. The intermediate so obtained can then be reacted,as described e.g. in WO 02/055509, with compounds of formulae

wherein R₁ to R₆, R₁₁, R₁₂, E₁ to E₄, X₁, X₂, Y₁ and Y₂ are as above,and then the basic N atoms are quaternised by known methods by reactionwith compounds of formulae R₁₀-LG, R₁₃-LG, R₁₄-LG and R₁₅-LG, whereinR₁₀, R₁₃, R₁₄ and R₁₅ are as defined above and LG is a leaving group.

Suitable compounds of formulae R₁₀-LG, R₁₃-LG, R₁₄-LG and R₁₅-LG areinter alia the customary alkylating agents known to the person skilledin the art. Examples thereof are alkyl or allyl halides, such as methyliodide or allyl chloride, dialkyl sulfates, such as dimethyl sulfate ordiethyl sulfate, or sulfonic acid esters, such as methyl tosylate ormethyl brosylate.

The starting compounds, the reaction conditions and the methods ofseparating and purifying the products are known to the person skilled inthe art.

The invention relates also to a process for the preparation ofsymmetrical compounds of formula (2), which process comprises reactingcyanuric chloride by known methods with, in succession in any order, acompound of formula (4)

a compound of formula (5)

and a compound of formula (6)

wherein M, A₁, E₁, X₁, R₃ and R₄ are as defined above.

The symmetrical compounds of formula (2) obtained by that process canreadily be converted into symmetrical compounds of formula (1) byreaction with the corresponding amines and subsequent quaternisation.

The present invention relates also to a process for the preparation ofsymmetrical compounds of formula (3), which process comprises reactingcyanuric chloride by known methods with, in succession in any order, acompound of formula (4)

a compound of formula (7)

and a compound of formula (8)

wherein M, A₃, E₁, R₂₀ and R₂₁ are as defined above.

A further aspect of the invention relates to a composition forbrightening synthetic or natural organic materials, comprising water, acompound of formula (1), (2) or (3) and optionally further adjuvants.

Such brightener compositions preferably comprise water and, based on thetotal weight of the formulation, 3–25% by weight, especially 5–15% byweight, of a brightener of formula (1) or (2) and 0–60% by weight,especially 5–50% by weight, adjuvants.

Suitable adjuvants are, for example, anionic or non-ionic dispersants,such as ethylene oxide adducts of fatty alcohols, higher fatty acids,alkyl phenols, ethylenediamine-ethylene oxide/propylene oxide adducts,N-vinylpyrrolidone/3-vinylpropionic acid copolymers, water retentionagents, such as ethylene glycol, glycerol or sorbitol, or biocides.

The compounds of formulae (1), (2) and (3) according to the inventionare especially suitable for the optical brightening of natural,semi-synthetic or synthetic textile fibres or of paper.

The novel bis(triazinylamino)stilbenes are preferably used for thetreatment of textile fibre materials, because, by virtue of their highabsorption capacity in both the UV-A and the UV-B range, there isobtained not only an excellent brightener action but also a considerableincrease in the sun-protection factor (SPF).

The invention therefore relates also to a method of increasing the SPFof a textile fibre material, which comprises treating the textile fibrematerial with 0.05–3.0% by weight, based on the weight of the textilefibre material, of one or more compounds of formula (1), (2) or (3).

The textile fibres which can be treated in accordance with the method ofthe invention can be natural or synthetic fibres and mixtures thereof.Examples of natural fibres are vegetable fibres, such as cotton,viscose, flax, rayon or linen, and animal fibres, such as wool, mohair,cashmere, angora and silk. Synthetic fibres are, for example, polyester,polyamide and polyacrylonitrile fibres. Preferred textile fibres arecotton, polyamide and wool fibres.

The textile fibres to be treated preferably have a density of less than200 g/cm² and have not previously been dyed in dark shades.

Depending upon the compound of formula (1), (2) or (3) used, thetreatment can advantageously be carried out in a neutral, acid oralkaline bath. The method is normally carried out in a temperature rangeof 20° C.–140° C., for example at or dose to the boiling point of theaqueous bath, e.g. at about 90° C.

The application of the optical brighteners, optionally in combinationwith the application of dyes, can be carried out by conventional methodsknown from textile dyeing, for example the exhaust process or thepad-dyeing process.

When the method according to the invention is combined with a textiletreatment or textile finishing process, such a combined treatment canadvantageously be carried out using suitable stable preparations thatcomprise the compound of formula (1), (2) or (3) in a concentration suchthat the desired SPF improvement is achieved.

In certain cases, the compounds of formula (1), (2) or (3) can berendered fully active by an after-treatment. Such an after-treatment maybe a chemical treatment, such as treatment with an acid, a thermaltreatment or a combined chemical/thermal treatment.

The compounds of formula (1), (2) or (3) can advantageously be used inadmixture with an extender, such as anhydrous sodium sulfate,Na₂SO₄.10H₂O, NaCl, Na₂CO₃, an alkali metal phosphate, such as sodium orpotassium orthophosphate, sodium or potassium pyrophosphate or sodium orpotassium tripolyphosphate.

In addition to the compounds of formula (1), (2) or (3), the brightenermixtures according to the invention may comprise customary additives.Examples of such additives are emulsifiers, perfumes, colorants,opacifiers, further fluorescent whiteners, bactericides, non-ionicsurfactants, fabric-care constituents, especially fabric conditioners,dirt-loosening or dirt-repellent constituents, water-proofing agents,anti-gelling agents, such as nitrites or nitrates of alkali metals,especially sodium nitrate, and corrosion inhibitors, such as sodiumsilicate.

The amount of each of those additives is preferably <2% and isespecially in the range of 0.01–1.0%, based on the weight of the fibresbeing treated.

The treatment method according to the Invention can also be carried outby washing the textile fibre material with a detergent that comprises atleast one compound of formula (1), (2) or (3).

The following Examples illustrate the invention.

I. PREPARATION EXAMPLES

I.1. Compound of Formula (100)

(a) Intermediate of Formula (100a)

400 g of ice-water and 120 g (0.65 mol) of cyanuric chloride dissolvedin 753 g of methyl ethyl ketone are introduced into a 2.5 literflat-flanged flask. Then, in the course of 70 min, 990 ml of a 12%solution of 4,4′-diaminostilbene-2,2′-disulfonic acid in soda water areslowly added dropwise at pH 4.5–5.0 so that no excess of disulfonic acidis formed. When the addition is complete, stirring is carried out for 10min at an internal temperature of 5–10° C. 107.3 g (0.65 mol) of4-aminobenzoic acid ethyl ester are then introduced into the resultingyellow-brown suspension in the course of 10 min at 5–20° C. and pH7.0–7.5.

The yellow suspension is heated to 72° C.; after half an hour, 11 ml of50% NaOH and after a further half an hour 47 ml of 50% NaOH are added.After 1.5 hours' stirring at 72° C., a further 2.5 g (0.015 mol) of4-aminobenzoic acid ethyl ester are added. After a further one hour'sstirring at 72° C., the mixture is allowed to cool. After being left tostand overnight, the reaction mixture is heated to 50° C. and filteredthrough a suction filter. The filter cake is washed with 5% NaClsolution, taken up in 2 liters of ethanol and stirred for 2 h. Afterleaving to stand overnight, the precipitate is filtered off, washed withethanol and acetone and dried in vacuo at 80° C., yielding 305.4 g(97.24%) of yellow crystals of the intermediate (100a), which discolourin air.

(b) Compound of Formula (100)

32.0 g (0.31 mol) of 3-dimethylamino-1-propylamine are introduced into a350 ml sulfonation flask equipped with a condenser and pH meter. At 50°C., 19.34 g (0.02 mol) of the intermediate of formula (100a) areintroduced. The mixture is then stirred for 3 h at 50–55° C., duringwhich time the yellow suspension becomes a solution. The mixture is thenheated for 3 h at 60° C. The mixture is then heated to 70° C. andstirred for 1.5 h. After being cooled to RT (room temperature), themixture is diluted with 25 ml of water, and the clear solution is leftto stand overnight. The solution is then diluted with water and adjustedto pH 1 with conc. hydrochloric acid. The precipitate is filtered offwith suction, taken up in 5% NaCl solution, filtered again at pH 4 andwashed with 5% NaCl solution and then dried in vacuo at 70° C.

Yield: 21.6 g

I.2. Compound of Formula (101)

32.0 g (0.31 mol) of 3-dimethylamino-1-propylamine are introduced into a100 ml sulfonation flask equipped with a condenser. At 60° C., 19.3 g(0.02 mol) of the intermediate of formula (100a) are introduced. Themixture is boiled under reflux (122–125° C.) for 24 h. After cooling toRT, the crude product is diluted with water and concentrated using arotary evaporator. That process is repeated twice. The pH is thenadjusted to 8.0 and the supernatant solution is poured off. The residueis suspended in 5% NaCl solution and acetone and stirred for 1 h. Theprecipitate is filtered off with suction, again taken up in acetone,filtered and washed with acetone. The crystals so obtained are dried invacuo at 70° C.

Yield: 20.2 g (87%)

I.3. Compound of Formula (102)

50 ml of water and 40 ml of 2N NaOH are heated at 70° C. in a 350 mlsulfonation flask. 10.0 g (8 mmol) of the compound of formula (101)prepared according to Example I.2 are added, there being formedinitially a yellow solution, then a two-phase mixture. After cooling to40° C., 8.0 g (0.064 mol) of dimethyl sulfate are added dropwise. Themixture is stirred for 2 h at 50° C.; then 10 ml of 2N NaOH and 2.0 g(0.016 mmol) of dimethyl sulfate are added. After being stirred for afurther 2.5 h at 50° C., the mixture is heated to 75° C. in order todestroy excess dimethyl sulfate. After cooling to RT and leaving tostand overnight, the supernatant solution is poured off, and the residueis suspended in 10% NaCl solution. The pH is adjusted to 8–9, thesupernatant solution is poured off and the residue is again suspended in10% NaCl solution. The solid is separated off in a centrifuge and driedin vacuo at 70° C.

Yield: 9.4 g (90%).

I.4. Compound of Formula (103)

20 g (0.327 mol) of ethanolamine are heated at 50° C. in a 100 mlsulfonation flask equipped with a condenser and pH meter. 10.5 g (0.01mol) of the compound of formula (100) prepared according to Example I.1are introduced in very small portions. The mixture is stirred for 5 h at120° C. and left to stand overnight. After addition of 50 ml of water,firstly a yellow solution and after a few minutes a two-phase mixture isobtained. The water is poured off and the residue is again suspended inwater at pH 6. The yellow precipitate is filtered off and washed with 5%NaCl solution. The residue is taken up in 5% NaCl solution and stirredat pH 6.0–6.5. The yellow crystals are filtered off, washed again with5% NaCl solution and dried in vacuo at 70° C.

Yield: 7.7 g (71%)

I.5. Compound of Formula (104)

In a 350 ml sulfonation flask equipped with a condenser and pH meter, 75g (0.84 mol) of 2-dimethylaminoethanol are heated at 45° C. 21.7 g(0.022 mol) of intermediate of formula (100a), prepared according toExample I.1, are introduced and the mixture is stirred for 1 h at 70° C.After being cooled to RT, the reaction mixture is poured into 300 ml ofacetone. The light-yellow supernatant solution is poured off and theresidue is again taken up in 300 ml of acetone. The now colourlesssupernatant solution is decanted off, and the residue is filtered,washed with acetone and suspended in 250 ml of water. After 30 minutes'stirring at pH 5.5, the light-yellow crystals are filtered off, washedwith water and dried in vacuo at 70° C.

Yield: 19.0 g (84%)

I.6. Compound of Formula (105)

(a) Intermediate of Formula (105a)

200 g of ice-water and 60 g (0.325 mol) of cyanuric chloride dissolvedin 465 ml of methyl ethyl ketone are introduced into a 2.5 literflat-flanged flask. Then, in the course of 40 min, 493 ml of a 12%solution of 4,4′-diaminostilbene-2,2′-disulfonic acid in soda water areslowly added dropwise at pH 4.5–5.0 so that no excess of disulfonic acidis formed. When the addition is complete, stirring is carried out for 10min at an internal temperature of 5–10° C. Using a metering pump, thesuspension so obtained is added dropwise in the course of 35 min at55–60° C. and pH 7.0–7.5 to a solution of 61.5 g (0.341 mol) of4-amino-N-(2-hydroxyethyl)benzamide in 450 ml of water. The mixture isthen stirred for 1 h at 60° C. and the methyl ethyl ketone is distilledoff at 90° C. After cooling to 70° C., the yellow crystals are filteredthrough a suction filter, washed with 2.5% NaCl solution and dried invacuo at 70° C.

Yield: 144.6 g

(b) Compound of Formula (105)

25.3 g (0.42 mol) of ethylenediamine in 150 ml water and 150 ml dioxaneare introduced into a 750 ml sulfonation flask equipped with a condenserand pH meter. At 70–75° C., 35.0 g (0.035 mol) of the intermediate offormula (105a) are introduced. The yellow solution is stirred for 1 h at86–88° C. After being cooled to 70° C., the solution is then dilutedwith 100 ml of water and adjusted to pH 4.0 with 75 ml of conc.hydrochloric acid. Stirring is continued for a further 1 h at 70° C. Theprecipitate is filtered through a suction filter and washed with a smallamount of water. The filter cake is again suspended in 500 ml of waterand dissolved at 70° C. and pH 10.9. The pH is then adjusted to 3.5 withconc. hydrochloric acid. The yellow crystals are filtered through asuction filter, washed three times with 5% NaCl solution and dried invacuo at 70° C.

Yield: 36.7 g

I.7. Compound of Formula (106)

36.2 g (0.35 mol) of diethylenetriamine in 150 ml water and 150 ml ofdioxane are introduced into a 750 ml sulfonation flask equipped with acondenser and pH meter. At 70–75° C., 35.0 g (0.035 mol) of theintermediate of formula (105a) prepared according to Example I.6 areintroduced. The yellow solution is stirred for 3.5 h at 86–88° C. Aftercooling to 70° C., the solution is then diluted with 100 ml of of waterand adjusted to pH 4.5 with 115 ml of conc. hydrochloric acid. Afterbeing cooled to RT, the mixture is stirred for a further 1 h. Theprecipitate is filtered through a suction filter and washed three timeswith 2.5% NaCl solution. The filter cake is again suspended in 500 ml ofwater. After adjustment to pH 5.3, the yellow crystals are filteredthrough a suction filter, washed with 2.5% NaCl solution and dried invacuo at 70° C.

Yield: 32.8 g (81%)

I.8. Compound of Formula (107)

43.0 g (0.33 mol) of 1-(2-aminoethyl)-piperazine in 150 ml of water and150 ml of dioxane are introduced into a 750 ml sulfonation flaskequipped with a condenser and pH meter. At 70–75° C., 35.0 g (0.035 mol)of the intermediate of formula (105a) prepared according to Example I.6are introduced. The yellow solution is stirred for 2 h at 86–88° C.After being cooled to 70° C., the solution is then diluted with 100 mlof water and adjusted to pH 4.0 with 65 ml of conc. hydrochloric acid.After being cooled to RT, the mixture is stirred for a further 1 h. Theprecipitate is filtered through a suction filter and washed with water.The filter cake is again suspended in 120 ml of water and 50 ml of 5%NaCl solution. After adjustment to pH 5.0–5.5, the mixture is stirredfor a further 4 h. The yellow crystals are then filtered through asuction filter, washed with 5% NaCl solution and dried in vacuo at 70°C.

Yield: 42.9 g

I.9. Compound of Formula (108)

19.1 g (0.15 mol) of 1-(2-hydroxyethyl)-piperazine in 100 ml of waterand 100 ml of dioxane are introduced into a 350 ml sulfonation flaskequipped with a condenser and pH meter. At 70–75° C., 35.0 g (0.025 mol)of the intermediate of formula (105a) prepared according to Example I.6are introduced. The yellow solution is stirred for 3 h at 86–88° C.After being cooled to 70° C., the solution is then diluted with 50 ml ofwater and adjusted to pH 5.0 with 15 ml of conc. hydrochloric acid.After cooling to RT, the precipitate is filtered through a suctionfilter and washed with water. The filter cake is again suspended in 250ml of water. After adjustment to pH 5, the mixture is stirred for afurther 1 h at 70° C. The yellow crystals are then filtered through asuction filter, washed with water and dried in vacuo at 70° C.

Yield: 25.8 g (90%)

I.10. Compound of Formula (109)

18.8 g (0.13 mol) of N,N-bis(3-aminopropyl)methylamine in 100 ml ofwater and 100 ml of dioxane are introduced into a 350 ml sulfonationflask equipped with a condenser and pH meter. At 70–75° C., 22.7 g(0.021 mol) of the intermediate of formula (105a) prepared according toExample I.6 are introduced. The yellow solution is stirred for 3 h at86–88° C. After cooling to 70° C., the solution is then diluted with 120ml of water and adjusted to pH 4.5 with 35 ml of conc. hydrochloricacid. After addition of 100 ml of acetone, the precipitate is filteredthrough a suction filter, washed with water and dried in vacuo at 70° C.

Yield: 28.7 g

I.11. Compound of Formula (110)

7.9 g (0.059 mol) of 1-(2-hydroxyethyl)-piperazine in 120 ml of waterand 120 ml of dioxane are introduced into a 750 ml sulfonation flaskequipped with a condenser and pH meter. At 70–75° C., 25.0 g (0.025 mol)of the intermediate of formula (100a) prepared according to Example I.1are introduced. The yellow solution is stirred for 3 h at 86–88° C.After being cooled to 70° C., the solution is adjusted to pH 4.5 with 10ml of conc. hydrochloric acid. After being cooled to RT, the mixture isstirred for a further 1 h. The precipitate is filtered through a suctionfilter and washed three times with water. The filter cake is againsuspended in 300 ml of water and the mixture is stirred at pH 5 for afurther 1 h. The yellow crystals are then filtered through a suctionfilter, washed with water and dried in vacuo at 70° C.

Yield: 25.2 g (90%)

I.12. Compound of Formula (111)

9.1 g (0.15 mol) of ethylenediamine in 120 ml of water and 120 ml ofdioxane are introduced into a 750 ml sulfonation flask equipped with acondenser and pH meter. At 70–75° C., 25.4 g (0.025 mol) of theintermediate of formula (100a) prepared according to Example I.1 areintroduced. The yellow solution is stirred for 4 h at 86–88° C. Afterbeing cooled to 70° C., the solution is adjusted to pH 4.5 with 18 ml ofconc. hydrochloric acid and left to stand overnight. After thesupernatant solution has been poured off, the residue is triturated in amortar, filtered through a suction filter, washed with water and driedin vacuo at 70° C.

Yield: 22.6 g (93%)

I.13. Compound of Formula (112)

100 ml (1 mol) of 2-dimethylaminoethanol are introduced into a 350 mlsulfonation flask equipped with a condenser and pH meter. At 70–75° C.,30.0 g (0.03 mol) of the intermediate of formula (105a) are introduced.The yellow suspension is stirred for 1 h at 110–115° C. After beingcooled to 90° C., the mixture is then diluted with 100 ml of water. Thesolution is concentrated using a rotary evaporator, and the residue isdissolved in 150 ml of water. The pH is adjusted to 4.5 by addition of20 ml of conc. hydrochloric acid. The precipitate is filtered through asuction filter, washed with water and dried in vacuo at 80° C.

Yield: 21.8 g (68%)

I.14. Compound of Formula (113)

5.9 g (0.045 mol) of 3-diethylaminopropylamine in 70 ml of water areintroduced into a 350 ml sulfonation flask equipped with a condenser andpH meter. At 70–75° C., 15.7 g (0.015 mol) of the intermediate offormula (105a) are introduced. The mixture is stirred for 4 h at 96–98°C. and after cooling to 70° C. is diluted with 100 ml of water. The pHis adjusted to 2.0 by addition of 7 ml of conc. hydrochloric add. Theprecipitate is filtered through a suction filter and washed with a smallamount of water. The filter cake is then suspended in 450 ml of waterand stirred for 2 h at RT. The precipitate is filtered through a suctionfilter, washed with 2.5% NaCl solution and dried in vacuo at 70° C.

Yield: 16.8 g (98%)

I.15. Compound of Formula (114)

(a) Intermediate of Formula (114a)

400 g of ice-water and 120 g (0.65 mol) of cyanuric chloride dissolvedin 753 g of methyl ethyl ketone are introduced into a 2.5 literflat-flanged flask equipped with a condenser, stirrer and pH meter.Then, in the course of 65 min, 990 ml of a 12% solution of4,4′-diaminostilbene-2,2′-disulfonic acid in soda water are slowly addeddropwise at pH 4.5–5.0 so that no excess of disulfonic acid is formed.When the addition is complete, stirring is carried out for a further 10min at an internal temperature of 5–10° C. Then, in the course of 15min, 90.3 g (0.65 mol) of 4-aminobenzamide are introduced at 10–20° C.and pH 7.0–7.5 into the resulting yellow suspension. The yellowsuspension is then heated to 72° C. in the course of one hour andstirred at that temperature for a further 2 h. After the solvent hasbeen distilled off, the mixture is stirred for 4 h at 85° C. and thenleft to stand overnight at RT. The crude product is filtered through asuction filter, washed with water and dried in vacuo at 80° C.

Yield: 327 g Appearance: yellow crystals

(b) Compound of Formula (114)

130 ml of water are introduced into a 350 ml sulfonation flask equippedwith a condenser and pH meter and, at 70–75° C., 30.0 g (0.033 mol) ofthe intermediate of formula (114a) are introduced. 13.0 g (0.098 mol) of1-amino-3-diethylaminopropane are then added dropwise. The yellowsuspension so obtained is stirred for 8 h at 96–97° C. and then left tostand overnight at RT. The pH is adjusted to 4.5 by addition of 12 ml ofconc. hydrochloric acid. The precipitate is filtered through a suctionfilter, washed with 200 ml of water and then dried in vacuo at 80° C.

Yield: 30.0 g (86%) Appearance: beige crystals

I.16. Compound of Formula (115)

(a) Intermediate of Formula (115a)

400 g of ice-water and 120 g (0.65 mol) of cyanuric chloride dissolvedin 753 g of methyl ethyl ketone are introduced into a 2.5 literflat-flanged flask equipped with a condenser, stirrer and pH meter.Then, in the course of 65 min, 977 ml of a 12% solution of4,4′-diaminostilbene-2,2′-disulfonic acid in soda water are slowly addeddropwise at pH 4.5–5.0 so that no excess of disulfonic acid is formed.When the addition is complete, stirring is carried out at an internaltemperature of 5–10° C. for a further 10 min. Then, in the course of 15min, 97.6 g (0.65 mol) of 4-amino-N-methylbenzamide are introduced at10–20° C. and pH 7.0–7.5 into the resulting yellow suspension. Theyellow suspension is then heated to 72° C. in the course of one hour andstirred at that temperature for a further 2 h. After the solvent hasbeen distilled off, a further 200 ml of water are added and the mixtureis stirred for a further 1.5 h at 85° C. After cooling to 75° C., thecrude product is filtered through a suction filter, washed with 2.5%NaCl solution and dried in vacuo at 80° C.

Yield: 306.1 g Appearance: yellow crystals

(b) Compound of Formula (115)

130 ml of of water are introduced into a 350 ml sulfonation flaskequipped with a condenser and pH meter and, at 70° C., 30.0 g (0.030mol) of the intermediate of formula (115a) are introduced. 12.1 g (0.091mol) of 1-amino-3-diethylaminopropane are then added dropwise. Theyellow suspension so obtained is stirred for 4 h at 96–97° C. Aftercooling to 70° C., the pH is adjusted to 4.5 by addition of 8 ml ofconc. hydrochloric acid. The precipitate is filtered off through asuction filter, washed with 200 ml of water and then dried in vacuo at80° C.

Yield: 32.5 g (100%) Appearance: yellow crystals

1. A compound of formula (1), (2) or (3)

wherein M is hydrogen, an alkali metal ion or an ammonium ion, A₁ is—OR₁, —NHR₁, N-morpholinyl or 1-piperidyl, A₂ is —OR₂, —NHR₂,N-morpholinyl or 1-piperidyl, E₁, E₂, E₃ and E₄ are each independentlyof the others —O—, —NH— or —NR₉—, wherein R₉ together with R₄, R₆, R₂ orR₁₂ forms an ethylene radical, R₁ to R₆, R₁₁ and R₁₂ are eachindependently of the others hydrogen, alkyl, alkoxy, aryl, aralkyl,alkoxyalkyl, hydroxyalkyl, aminoalkyl or a group of the formula—(C_(n)H_(2n)Y)_(m)—R₇, wherein Y is —O—, —NH—, —NR₈—, —CONH— or—CONR₈—, R₇ is hydrogen, alkyl or aryl and R₈ is alkyl or aryl, n is anumber from 2 to 6 and m is a number from 1 to 10, or pairs of tworadicals R₁ and R₂, R₃ and R₄, R₅ and R₆ or R₁₁ and R₁₂ together form abivalent radical of the formula —CH₂CH₂OCH₂CH₂— or, when E₁, E₂, E₃ orE₄ is —NR₉—, R₄, R₆, R₂ or R₁₂ together with R₉ forms an ethyleneradical, R₁₀, R₁₃, R₁₄ and R₁₅ are each independently of the othersalkyl, alkenyl, aryl or aralkyl, X₁ and X₂ are each independently of theother 1,2-cyclohexanediyl, a group of the formula —(C_(n)H_(2n))_(m)— ora group of the formula —(C_(n)H_(2n)Y)_(m)—, wherein Y is —O—, —NH—,—NR₈—, —CONH— or —CONR₈— and R₈ is alkyl or aryl, n is a number from 2to 6 and m is a number from 1 to 10, Y₁ and Y₂ are each independently ofthe other 1,2-cyclohexanediyl, a group of the formula—(C_(n)H_(2n))_(m)— or a group of the formula —(C_(n)H_(2n)Y)_(m)—,wherein Y is —O—, —NH—, —NR₈—, —CONH— or —CONR₈— and R₈ is alkyl oraryl, n is a number from 2 to 6 and m is a number from 1 to 10 and A⁻ isa singly charged anion or the two A⁻ form a doubly charged anion, R₁₆,R₁₇, R₁₈ and R₁₉ are each independently of the others hydrogen,2-hydroxyethyl, 2-aminoethyl or 3-aminopropyl, R₂₀, R₂₁, R₂₂ and R₂₃ areeach independently of the others alkyl, and A₃ and A₄ are2-hydroxyethylamino, 3-dimethylaminopropylamino or3-diethylaminopropylamino.
 2. A compound of formula (2) or (3) accordingto claim 1, wherein the substituents A₁ and A₂, A₃ and A₄, E₁ and E₂, X₁and X₂, R₁₆ and R₁₈, R₁₇ and R₁₉, R₂₀ and R₂₂ and also R₂₁ and R₂₃ arein each case identical.
 3. A compound of formula (1) according to claim1, wherein the substituents E₁ and E₂, E₃ and E₄, X₁ and X₂, Y₁ and Y₂,R₃ and R₅, R₄ and R₆, R₁₄ and R₁₅, R₁ and R₁₁, R₂ and R₁₂ and also R₁₀and R₁₃ are in each case identical.
 4. A compound of formula (1) or (2)according to claim 1, wherein X₁ and X₂ are ethylene or trimethylene. 5.A compound of formula (3) according to claim 1, wherein R₂₀, R₂₁, R₂₂and R₂₃ are methyl or ethyl.
 6. A compound of formula (2) or (3)according to claim 1, wherein A₁, A₂, A₃ and A₄ are amino, methylamino,2-hydroxyethylamino, 3-dimethylaminopropylamino or ethoxy.
 7. A compoundof formula (1) according to claim 1, wherein R₁ to R₆ and R₁₀ to R₁₅ aremethyl.
 8. A process for the preparation of a compound of formula (2)according to claim 1 wherein the substituents A₁ and A₂, A₃ and A₄, E₁and E₂, X₁ and X₂, R₁₆ and R₁₈, R₁₇ and R₁₉, R₂₀ and R₂₂ and also R₂₁and R₂₃ are in each case identical, which process comprises reactingcyanuric chloride by known methods with, in succession in any order, acompound of formula (4)

a compound of formula (5)

and a compound of formula (6)

wherein M, A₁, E₁, X₁, R₃ and R₄ are as defined in claim
 1. 9. A processfor the preparation of a compound of formula (3) according to claim 1wherein the substituents A₁ and A₂, A₃ and A₄, E₁ and E₂, X₁ and X₂, R₁₆and R₁₈, R₁₇ and R₁₉, R₂₀ and R₂₂ and also R₂₁ and R₂₃ are in each caseidentical, which process comprises reacting cyanuric chloride by knownmethods with, in succession in any order, a compound of formula (4)

a compound of formula (7)

and a compound of formula (8)

wherein M, A₃, E₁, R₂₀ and R₂₁ are as defined in claim
 1. 10. A methodfor the optical brightening of natural, semi-synthetic or synthetictextile fibres, which comprises treating said fibres in an aqueousmedium with an effective amount of a compound of formula (1), (2) or (3)according to claim
 1. 11. A method for the optical brightening of paper,which comprises treating said paper fibres in an aqueous medium with aneffective amount of a compound of formula (1), (2) or (3) according toclaim
 1. 12. A method of increasing the SPF of a textile fibre material,comprising the treatment of the textile fibre material with 0.05–3.0% byweight, based on the weight of the textile fibre material, of one ormore compounds of formula (1), (2) or (3) according to claim
 1. 13. Acomposition for brightening synthetic or natural organic materials,comprising water, a compound of formula (1), (2) or (3) according toclaim 1 and optionally further adjuvants.